JP2013234350A - Apparatus and method for manufacturing substrate with intermediate layer for oxide superconductive wire rod - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for manufacturing a substrate with an intermediate layer for an oxide superconductive wire rod, capable of manufacturing, in a shorter time, the substrate with the intermediate layer including multiple layers.SOLUTION: An apparatus is for manufacturing a substrate with an intermediate layer for an oxide superconductive wire rod, in which an intermediate layer having a multiple layer structure is formed on a long oriented metal substrate 21 using a gas phase growing method. In the apparatus for manufacturing the substrate with the intermediate layer for the oxide superconductive wire rod, a multi-target 15 including a plurality of sputter targets is disposed in a film forming apparatus 13, and targets corresponding to respective layers constituting the intermediate layer are provided in the multi-target from the upstream to the downstream in the transporting direction of the oriented metal substrate in the order of film deposition.

Description

  The present invention relates to an apparatus and a method for manufacturing a substrate with an intermediate layer for an oxide superconducting wire.

  Since the discovery of high-temperature superconductors that have superconductivity at the temperature of liquid nitrogen, development of high-temperature superconducting wires aimed at application to power devices such as cables, current limiters, and magnets has been actively conducted. Among them, an oxide superconducting wire in which an oxide superconducting layer such as RE123 (RE: rare earth element) oriented on a metal substrate is attracting attention.

  A general structure of such an oxide superconducting wire is schematically shown in FIG. As shown in FIG. 6, the oxide superconducting wire 2 is manufactured by sequentially laminating an intermediate layer 22 and an oxide superconducting layer 23 on an oriented metal substrate 21. In addition, a protective layer, a stabilization layer, etc. may be laminated | stacked as needed (patent document 1, 2).

  The intermediate layer 22 is a ceramic layer provided for growing a c-axis oriented oxide superconductor crystal on the oriented metal substrate 21 to form the oxide superconducting layer 23. As shown in FIG. It is composed of a plurality of ceramic layers.

For example, in FIG. 6, an yttria (Y ₂ O ₃ ) layer or a ceria (CeO ₂ ) layer as a seed layer (seed film layer) 22 a for forming a c-axis oriented ceramic layer on an oriented metal substrate 21. The yttria-stabilized zirconia (YSZ) layer as a barrier layer (diffusion prevention layer) 22b for preventing the diffusion of the metal element contained in the oriented metal substrate 21, the metal constituting the oriented metal substrate 21 and the oxide superconductor An intermediate layer 22 having a three-layer structure formed in the order of a CeO ₂ layer as a cap layer (lattice matching layer) 22c for matching the lattice constant is used.

  These intermediate layers are formed by vapor phase growth methods such as sputtering, electron beam evaporation (EBD), and pulsed laser vapor deposition (PLD). Among these methods, stable production, cost From this point of view, the RF sputtering method is generally employed.

JP 2007-80780 A JP 2007-311234 A

  However, conventionally, since these layers were formed one by one, there was a problem that it took a long time to form the intermediate layer.

  That is, in the conventional intermediate layer formation, after the film formation of one layer is completed, the temperature of the film formation heater is once lowered to a temperature at which exposure to the atmosphere is possible, the apparatus is exposed to the atmosphere, and the target is It was necessary to replace it. After the replacement of the target, the next layer is formed by evacuating the film formation apparatus and raising the temperature of the film formation heater again. For this reason, it takes a long time to form an intermediate layer having a multilayer structure.

  Accordingly, the present invention provides an apparatus and a method for manufacturing a substrate with an intermediate layer for an oxide superconducting wire capable of manufacturing a substrate with an intermediate layer provided with a multilayer intermediate layer in a shorter time. Is an issue.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have completed the present invention. Hereinafter, the present invention will be described for each claim.

The invention described in claim 1
An apparatus for manufacturing a substrate with an intermediate layer for an oxide superconducting wire that forms an intermediate layer of a multilayer structure using a vapor phase growth method on a long oriented metal substrate,
A multi-target provided with a plurality of targets is arranged in a film forming apparatus,
The multi-target is provided with targets corresponding to the respective layers constituting the intermediate layer in order of film formation from the upstream side to the downstream side in the transport direction of the oriented metal substrate. It is a manufacturing apparatus of the base material with an intermediate | middle layer for wires.

  In the invention of this claim, the multi-target in which the targets corresponding to the respective layers constituting the intermediate layer are provided in the order of film formation from the upstream side to the downstream side in the conveying direction of the oriented metal substrate is provided in the film forming apparatus Therefore, an intermediate layer having a predetermined multilayer structure can be formed on the oriented metal substrate only by passing the oriented metal substrate once through the film forming apparatus.

  For this reason, there is no need to provide steps for cooling and heating the film formation heater, exposing to the atmosphere, and replacing the target for each film formation, and an intermediate layer in which an intermediate layer having a multilayer structure is formed in a shorter time. An attached base material can be manufactured.

  In addition, it is preferable to provide a partition plate (slit) at the boundary of each target so as to control the deposition of each layer with certainty.

The invention described in claim 2
An apparatus for manufacturing a substrate with an intermediate layer for an oxide superconducting wire that forms an intermediate layer of a multilayer structure using a vapor phase growth method on a long oriented metal substrate,
The deposition apparatus for each layer provided with a target corresponding to each layer constituting the intermediate layer is connected and arranged in the order of deposition from the upstream side to the downstream side in the transport direction of the oriented metal substrate. Is an apparatus for manufacturing a substrate with an intermediate layer for an oxide superconducting wire.

  In the present invention, the film forming apparatus for each layer provided with targets corresponding to the respective layers constituting the intermediate layer is connected in the order of film formation from the upstream side to the downstream side in the transport direction of the oriented metal substrate. Therefore, an intermediate layer having a predetermined multilayer structure can be formed on the oriented metal substrate by sequentially passing through these film forming apparatuses.

  For this reason, as described above, there is no need to provide a process for cooling and heating the film formation heater, exposing to the atmosphere, and replacing the target for each film formation, and an intermediate layer having a multilayer structure can be formed in a shorter time. The intermediate substrate with an intermediate layer can be produced.

The invention according to claim 3
An oxidation layer characterized in that an intermediate layer having a multilayer structure is formed on a long oriented metal substrate using the apparatus for manufacturing a substrate with an intermediate layer for an oxide superconducting wire according to claim 1 or 2. It is a manufacturing method of the base material with an intermediate | middle layer for object superconducting wires.

  By using the above-described apparatus for manufacturing a substrate with an intermediate layer for each oxide superconducting wire, it is necessary to provide a process of cooling or heating a film formation heater, exposure to the atmosphere, and target replacement for each film formation. Therefore, a substrate with an intermediate layer in which an intermediate layer having a multilayer structure is formed in a shorter time can be produced.

The invention according to claim 4
The base with an intermediate layer for an oxide superconducting wire according to claim 3, wherein the thickness of each film-forming layer is adjusted by adjusting the width of each target corresponding to each layer constituting the intermediate layer. It is a manufacturing method of material.

  By adjusting the width of each target and adjusting the thickness of each film formation layer, an intermediate layer having a multilayer structure in which film formation layers of a desired thickness are stacked while transporting a metal substrate at a constant transport speed Can be easily manufactured in a short time.

  The “target width” refers to the width of the target in the transport direction of the metal substrate.

The invention described in claim 5
4. The method for producing a substrate with an intermediate layer for an oxide superconducting wire according to claim 3, wherein the thickness of each film-forming layer is adjusted by adjusting the conveyance speed of the metal substrate.

  By adjusting the transport speed of the metal substrate and adjusting the thickness of each film formation layer, it is easy to quickly form an intermediate layer of a multilayer structure in which film formation layers with a desired thickness are laminated as described above. Can be manufactured.

  According to the present invention, there are provided an apparatus and a method for manufacturing a substrate with an intermediate layer for an oxide superconducting wire capable of manufacturing a substrate with an intermediate layer provided with a multilayer intermediate layer in a shorter time. Can do.

It is a figure which shows typically an example of a structure of the manufacturing apparatus of the base material with an intermediate | middle layer of embodiment of this invention. It is a perspective view which shows typically an example of the multi target used for manufacture of the base material with an intermediate | middle layer of embodiment of this invention. It is a perspective view which shows typically another example of the multi target used for manufacture of the base material with an intermediate | middle layer of embodiment of this invention. It is a top view which shows typically another example of the multi target used for manufacture of the base material with an intermediate | middle layer of embodiment of this invention. It is a figure which shows typically another example of a structure of the manufacturing apparatus of the base material with an intermediate | middle layer of embodiment of this invention. It is sectional drawing which shows typically the structure of the thin film superconducting wire using the base material with an intermediate | middle layer. It is a perspective view which shows typically the target used for manufacture of the base material with a conventional intermediate | middle layer.

  Hereinafter, the present invention will be described based on embodiments.

(First embodiment)
The first embodiment is an apparatus for manufacturing a substrate with an intermediate layer in which a multi-target provided with a target corresponding to each layer constituting the intermediate layer is arranged in a film forming apparatus.

1. Manufacturing apparatus for substrate with intermediate layer (1) Manufacturing apparatus First, a manufacturing apparatus for a substrate with intermediate layer will be described. FIG. 1 is a diagram schematically showing the configuration of an intermediate layer-coated substrate manufacturing apparatus 1 according to the present embodiment. In FIG. 1, 11 is an unwinding device, 12 is a film formation heater, and 13 is A film forming apparatus 14 is a winding apparatus. These devices are housed in a vacuum chamber (not shown). Reference numeral 15 is a multi-target, and 21 is a metal substrate.

When forming the intermediate layer, the inside of the vacuum chamber is adjusted to, for example, an Ar / O ₂ mixed gas atmosphere of about 0.5 to ₂ Pa. The long metal substrate 21 is transported from the unwinding device 11 to the winding device 14 at a predetermined transport speed in a reel-to-reel manner.

  The metal substrate 21 unwound from the unwinding device 11 is first transported to the film forming heater 12, heated to a predetermined temperature, specifically about 700 ° C., and then transported to the film forming device 13.

  In the film forming apparatus 13, a multi-target in which three targets 15a, 15b, and 15c are arranged on a backing plate 15d is set. The three targets 15a, 15b, and 15c correspond to the first layer, the second layer, and the third layer of the intermediate layer, respectively, from the upstream side to the downstream side in the transport direction of the oriented metal substrate, Arranged in the order of film formation.

  With this arrangement, the first to third layers can be formed on the metal substrate 21 being transported (the lower surface in the drawing) by passing the oriented metal substrate once through the film forming apparatus 13. The layers can be continuously formed in the order of the layers, and an intermediate layer having a predetermined multilayer structure can be formed easily and in a short time.

  That is, it is unnecessary to perform cooling and heating of the film formation heater, exposure to the atmosphere, replacement of targets, etc. for each film formation as in the prior art. Shortening can be achieved.

  In addition, since the multi-target is arranged in one film forming apparatus, it is possible to make the manufacturing apparatus for the base material with an intermediate layer compact.

(2) Target FIGS. 2 to 4 show an example of the multi-target. FIG. 2 shows a multi-target used when forming a three-layer intermediate layer, and FIG. 3 shows a multi-target used when forming a two-layer intermediate layer.

  These targets are arranged without a gap so that the backing plate 15d is not sputtered.

Further, as shown in FIG. 4, partitions S ₁ and S ₂ made of a material that does not evaporate at the time of film formation such as sputtering, for example, stainless steel or oxide, are provided between the targets 15a, 15b, and 15c. May be. By providing such a partition, it is possible to reliably fill the gaps between the targets and to reliably suppress formation of a layer in which a plurality of target materials are mixed during film formation.

(Second Embodiment)
The second embodiment is an apparatus for manufacturing a base material with an intermediate layer in which a film forming apparatus for each layer provided with a target corresponding to each layer constituting the intermediate layer is connected and arranged.

  FIG. 5 is a diagram schematically showing the configuration of the intermediate layer-attached substrate manufacturing apparatus 1 according to the second embodiment. In the present embodiment, the film forming apparatus 13 includes three film forming apparatuses 13a, 13b, 13c, which are formed from the upstream side to the downstream side in the transport direction of the alignment metal substrate. Arranged in film order.

  Since each film forming apparatus is arranged in this manner, an intermediate layer having a predetermined multilayer structure can be formed on the oriented metal substrate by sequentially passing the metal substrate 21 through these film forming apparatuses. It is possible to form an intermediate layer having a predetermined multilayer structure easily and in a short time.

  And since the film-forming apparatus is arrange | positioned for every target, the film-forming conditions of each layer can be changed and set easily.

2. Next, the manufacturing method of a base material with an intermediate layer will be described. In the following description, an example in which an intermediate layer having a three-layer structure is formed using a manufacturing apparatus including a film forming apparatus in which a multi-target is arranged as a manufacturing apparatus for a substrate with an intermediate layer will be described. doing.

(1) Metal substrate First, a metal substrate is prepared. As the metal substrate, a long and flexible tape-shaped oriented metal substrate having a thickness of 0.05 to 200 μm is used. Specifically, Ni—Fe alloy, stainless steel, other alloys containing Ni, Cu and copper alloys, and a clad substrate in which these are combined are used. Among them, a clad material substrate is preferable. For example, a Ni / Cu / SUS clad substrate provided with a Ni layer is preferable because an intermediate layer having excellent orientation can be formed.

(2) Formation of intermediate layer Next, the intermediate layer is formed on the surface of the metal substrate using a manufacturing apparatus for a substrate with intermediate layer. Specifically, for example, an intermediate layer having a thickness of 0.3 to 2.0 μm and a three-layer structure of CeO ₂ / YSZ / Y ₂ O ₃ is formed.

The thickness of each of these layers is adjusted using, for example, the methods shown in (a) to (c) below. As described above, FIG. 2 is a multi-target used when forming an intermediate layer having a three-layer structure. In FIG. 2, l is the width of the multi-target 15, and la, lb, and lc are the targets. It is the width of 15a, 15b, 15c. Incidentally, as shown in FIG. 4, there is a case where the slits S _1, S ₂ to each target is provided.

A. Method of changing target width One method is to adjust the width of each target. That is, by adjusting the widths la, lb, and lc of each target, it is possible to adjust each film formation layer to a desired thickness while transporting the metal substrate at a constant transport speed.

B. Adjustment of conveyance speed Another method is a method of adjusting the conveyance speed of the metal substrate. That is, each film-forming layer can be adjusted to a desired thickness by adjusting the conveyance speed of the metal substrate.

C. Use of a slit plate Another method is to use a slit plate with holes. That is, each film-forming layer can be adjusted to a desired thickness by adjusting the shape and size of the hole in the slit plate provided between the target and the substrate.

  Next, based on an Example, it demonstrates more concretely.

(Example)
A three-layer structure in which Y ₂ O ₃ / YSZ / CeO ₂ is formed in this order from the metal substrate side in one film formation by RF sputtering using the intermediate layer-coated substrate manufacturing apparatus shown in FIG. A substrate with an intermediate layer on which an intermediate layer was formed was produced.

1. Metal substrate A metal substrate 21 made of Ni / Cu / SUS clad having a thickness of 100 μm, a width of 30 mm, and a length of 40 m was used.

2. Multi-target The multi-target 15 shown in FIG. 2 was used. The width l was set to 400 mm, and this was divided into _three by a Y ₂ O ₃ target 15a, a YSZ target 15b, and a CeO ₂ target 15c. The target thickness was 10 mm.

3. Formation of Intermediate Layer After the metal substrate 21 was heated to 700 ° C. by the film formation heater 12, it was transferred to the film formation apparatus 13 to form an intermediate layer having a three-layer structure under the following conditions.

Deposition temperature: 700-750 ° C
Atmosphere: Ar / O ₂ mixed gas with a pressure of 1 Pa RF power: 1 kW
Deposition rate: 17 mm / min
Metal substrate transfer speed: 3m / h

(Comparative example)
Using a conventional single target, that is, a Y ₂ O ₃ target, a YSZ target, and a CeO ₂ target each having a width of 133 mm, each layer was formed by changing the target for each film formation. Except for the above, an intermediate layer having a three-layer structure was formed under the same conditions as in the example.

4). Formed Intermediate Layer The thickness of each of the intermediate layers formed according to the examples is 100 nm for the Y ₂ O ₃ layer, 400 nm for the YSZ layer, and 100 nm for the CeO ₂ layer (total thickness: 600 nm). There was little difference with the intermediate layer made. However, the time required for forming the intermediate layer was 30 hours in the example, whereas it was 10 hours in the comparative example.

  From the above, it was confirmed that by applying the present invention, an intermediate layer equivalent to the intermediate layer formed by the conventional method can be formed in a much shorter time than the conventional method.

  While the present invention has been described based on the embodiments, the present invention is not limited to the above embodiments. Various modifications can be made to the above-described embodiments within the same and equivalent scope as the present invention.

DESCRIPTION OF SYMBOLS 1 Manufacturing apparatus of base material with intermediate layer 2 Oxide superconducting wire 11 Unwinding apparatus 12 Film forming heater 13 Film forming apparatus 14 Winding apparatus 15 Multi target 15d Backing plate 16 Target 21 Metal substrate 22 Intermediate layer 23 Oxide superconducting layer l Intermediate layer width S ₁ , S ₂ slit

Claims (5)

An apparatus for manufacturing a substrate with an intermediate layer for an oxide superconducting wire that forms an intermediate layer of a multilayer structure using a vapor phase growth method on a long oriented metal substrate,
A multi-target provided with a plurality of targets is arranged in a film forming apparatus,
The multi-target is provided with targets corresponding to the respective layers constituting the intermediate layer in order of film formation from the upstream side to the downstream side in the transport direction of the oriented metal substrate. An apparatus for manufacturing a substrate with an intermediate layer for a wire. An apparatus for manufacturing a substrate with an intermediate layer for an oxide superconducting wire that forms an intermediate layer of a multilayer structure using a vapor phase growth method on a long oriented metal substrate,
The deposition apparatus for each layer provided with a target corresponding to each layer constituting the intermediate layer is connected and arranged in the order of deposition from the upstream side to the downstream side in the transport direction of the oriented metal substrate. The manufacturing apparatus of the base material with an intermediate | middle layer for oxide superconducting wires characterized by these.   An oxidation layer characterized in that an intermediate layer having a multilayer structure is formed on a long oriented metal substrate using the apparatus for manufacturing a substrate with an intermediate layer for an oxide superconducting wire according to claim 1 or 2. The manufacturing method of the base material with an intermediate | middle layer for object superconducting wire.   The base with an intermediate layer for an oxide superconducting wire according to claim 3, wherein the thickness of each film-forming layer is adjusted by adjusting the width of each target corresponding to each layer constituting the intermediate layer. A method of manufacturing the material.   The method for producing a substrate with an intermediate layer for an oxide superconducting wire according to claim 3, wherein the thickness of each film-forming layer is adjusted by adjusting the transport speed of the metal substrate.

Images